Aqueous herbicidal composition based on a suspension concentrate comprising herbicides and safeners

ABSTRACT

The present invention relates to an aqueous herbicidal composition based on a suspension concentrate comprising 
 
a herbicidally active compound of the formula (I),  
                 
 
a safener of the formula (II)  
                 
 
and optionally a herbicidally active compound of the formula (III)  
                 
 
     In these formulae, R 1 , R 2 , R 3  and R 4  independently of one another are methyl or ethyl; R 5  is isopropyl or cyclopropyl; R 6  is hydrogen or chlorine; Q is cyclohexane-1,3-dion-2-yl, isoxazol-4-yl or pyrazol4yl; and 
         R 7 , R 8  and R 9  are hydrogen, halogen or various organic radicals.

The present invention relates to the field of crop protectionformulations. In particular, the invention relates to

-   -   herbicidal compositions comprising at least one herbicidally        active compound from the group of the inhibitors of acetolactate        synthetase, a herbicidally active compound from the group of the        inhibitors of hydroxyphenylpyruvate dioxygenase and at least one        safener from the group of the acylsulfonamides, and    -   formulations in the form of aqueous suspension concentrates        comprising at least one herbicidally active compound from the        group of the inhibitors of acetolactate synthetase and at least        one safener from the group of the acylsulfonamides.

Herbicidally active compounds are generally not employed in their pureform. Depending on the area of use and the type of application, and onphysical, chemical and biological parameters, the active compounds areemployed as an active compound formulation in a mixture with customaryauxiliaries and additives. Many herbicides display unwanted phytotoxicproperties against useful plants. To increase the herbicidal activityagainst a large number of unwanted plants, the combined application ofat least two herbicidally active compounds may be expedient. In somecases, this results in synergistic effects.

To avoid unwanted phytotoxic side-effects, it is known to applyherbicides in combination with a safener. Safeners are compounds which,fully or predominantly, prevent the phytotoxic side-effects ofherbicides in useful plants.

Thus, WO 03/026427 discloses inter alia the mixtures of the herbicidallyactive compounds of the formula (I),

in which the radicals R¹ to R⁴ are essentially alkyl,

-   and safeners of the formula (II)-   in which R⁵ is essentially alkyl or cycloalkyl and R⁶ is essentially    hydrogen, alkyl or halogen.

Mixtures of the herbicidally active compounds of the formula (I) withother herbicidally active compounds, inter alia isoxaflutole, are knownfrom WO 03/026426.

The combination of thiencarbazone-methyl, i.e. the compound of theformula (I) in which R¹ to R⁴ are each methyl, with cyprosulfamide, i.e.the compound of the formula (II) in which R⁵ is cyclopropyl and R⁶ ishydrogen, and isoxaflutole, i.e. the compound of the formula (III) inwhich Q is Q², R⁷ is methylsulfonyl, R⁸ is hydrogen and R⁹ istrifluoromethyl, is known from WO 2005/087006.

The combinations of

-   a) thiencarbazone-methyl with cyprosulfamide and pyrasulfotole, i.e.    the compound of the formula (III) in which Q is Q³, R⁷ is    methylsulfonyl, R⁸ is hydrogen and R⁹ is trifluoromethyl, and-   b) thiencarbazone-methyl with cyprosulfamide and tembotrione, i.e.    the compound of the formula (III) in which Q is Q¹, R⁷ is chlorine,    R⁸ is 2,2,2-trifluoroethoxymethyl and R⁹ is ethylsulfonyl, are known    from WO 2005/087004.

All of the active compounds referred to above and below by their commonname are also known, for example, from “The Pesticide Manual”, 13thedition, The British Crop Protection Council and the Royal Soc. ofChemistry, 2003, and from the website http://www.hclrss.demon.co.uk.

The mixtures mentioned of herbicidally active compounds of the formula(I) and safeners of the formula (II) have good herbicidal activity, inparticular for the control of unwanted plants in crops of corn; however,in practice they do not always have satisfactory properties, such as,for example, insufficient action against unwanted plants and/or lack ofcompatibility with useful plants, in particular in corn. Furthermore,for example, the storage stability of such mixtures is not alwayssufficient. The fact that, when the user dilutes the mixture to obtain aspray liquor, the two active compounds are not always homogeneouslydistributed therein, in particular when the mixture is not to be dilutedin water, but in a concentrated aqueous solution of fertilizers, has tobe considered a further disadvantage. Users increasingly demand thepossibility for dilution in a concentrated aqueous solution offertilizers.

It was an object of the present invention to provide a crop protectionformulation of the herbicidally active compounds of the formula (I) incombination with safeners of the formula (II) and optionally a furtherherbicide from the group of the inhibitors of hydroxyphenylpyruvatedioxygenase, with these crop protection formulations having high storagestability and, after dilution with concentrated aqueous solutions offertilizers, a homogeneous distribution of the active compounds.

This object is achieved by the special suspension concentrate of thepresent invention.

Accordingly, the present invention relates to an aqueous suspensionconcentrate, comprising

-   A) a herbicidally active compound of the formula (I) (component A),-    in which-    R¹, R², R³ and R⁴ independently of one another are methyl or ethyl,-   B) a safener of the formula (II) (component B),-    in which-    R⁵ is isopropyl or cyclopropyl and-    R⁶ is hydrogen or chlorine,-   C) optionally a herbicidally active compound of the formula (III)    (component C),-    in which-    Q is a radical Q¹, Q² or Q³,-    R⁷ is chlorine, methylsulfonyl or trifluoromethyl,-    R⁸ is hydrogen or 2,2,2-trifluoroethoxymethyl,-    R⁹ is methylsulfonyl or trifluoromethyl,-   D) dispersants and-   E) water.

Herbicidally active compounds of the formula (I) are known, for example,from WO 01/05788. Safeners of the formula (II) are known, for example,from U.S. Pat. No. 6,251,827. Herbicidally active compounds of theformula (III) in which Q is Q¹ are known, for example, from U.S. Pat.No. 6,376,429. Active compounds of the formula (III) in which Q is Q²are known, for example from EP 0 527 036. Active compounds of theformula (III) in which Q is Q³ are known, for example, from U.S. Pat.No. 6,420,317.

The aqueous suspension concentrates according to the invention have highstorage stability and, on dilution with water or else with concentratedaqueous solutions of fertilizers, a homogeneous distribution of theactive compounds, and do not tend to block spray nozzles.

The active compounds of the formulae (I), (II) and (III) in thesuspension concentrates according to the invention may also be presentin the form of their salts. Suitable salts are those described in thepublications WO 01/05788, U.S. Pat. No. 6,251,827, U.S. Pat. No.6,376,429, EP 0 527 036 and U.S. Pat. No. 6,420,317, in particular thealkali metal, alkaline earth metal and ammonium salts. Accordingly,unless indicated otherwise, in the present application the terms“herbicidally active compound of the formula (I)” or “formula (III)” and“safener of the formula (II)” are in each case meant to include both thepure compound and its respective salt, in particular the sodium salt.

The aqueous suspension concentrates according to the invention mayadditionally comprise further auxiliaries and additives customary incrop protection, in particular

F) antifreeze agents

G) preservatives

H) defoamers

I) thickeners and thixotropic agents.

In addition, they may also comprise further substances, such ascolorants and fragrances, and antidrift agents, tackifiers andpenetrants, evaporation inhibitors, and also agents for adjusting the pHand the viscosity.

Suitable dispersants are, for example, ionic and nonionic dispersants,for example:

-   1) tristyrylphenol polyethylene glycol phosphoric esters, for    example Dispergon® LFH (Clariant), CAS No. 114535-82-9,-   2) alkyl polyglycosides, such as C₉- to C₁₁-alkyl glucopyranosides,    for example those of the Agniqu® PG series 9116 (Cognis),-   3) alkyl polyglucosides, for example AL 2575 (Uniqema), CAS No.    68515-73-1.-   The total proportion of dispersants in the suspension concentrates    according to the invention is generally between 0.5 and 20% by    weight. If the dispersants, in addition to their dispersing    properties, are also used for increasing the biological    effectiveness, for example as penetrants or tackifiers, their    proportion in the suspension concentrates according to the invention    may increase to up to 30% by weight.

Suitable antifreeze agents are those from the group of the ureas, diolsand polyols, such as ethylene glycol and propylene glycol. Theproportion of antifreeze agents in the suspension concentrates accordingto the invention is generally between 1 and 15% by weight, in particularbetween 2 and 10% by weight.

Suitable preservatives are those from the group of the isothiazoles,such as 2-methyl-2H-isothiazol-3-one, 1,2-benzisothiazol-3(2H)-one andthe sodium salt. The proportion of preservatives in the suspensionconcentrates according to the invention is generally between 0.05 and 1%by weight, in particular between 0.05 and 0.5% by weight.

Suitable defoamers are, for example, those based on silicones, inparticular polydimethylsiloxanes, preferably Rhodorsil® 481. Theproportion of defoamers in the suspension concentrates according to theinvention is generally between 0.05 and 1% by weight, in particularbetween 0.1 and 0.5% by weight.

Suitable thickeners and thixotropic agents are, for example:

-   1) modified natural silicates, such as chemically modified    bentonites, hectorites, attapulgites, montmorillonites, smectites or    other silicate minerals, such as Bentonee® (Elementis), Attagel®    (Engelhard), Agsorb® (Oil-Dri Corporation) or Hectorite® (Akzo    Nobel),-   2) natural and synthetic silicates, such as silicates of the    Sipernat®, Aerosil® or Durosil® series (Degussa), the CAB-O-SIL®    series (Cabot) or the Van Gel series (R. T. Vanderbilt),-   3) thickeners based on synthetic polymers, such as thickeners of the    Thixin® or Thixatrol® series (Elementis).

Preferred thickeners and thixotropic agents are, for example, modifiedphyllosilicates and natural and synthetic silicates. The proportion ofthickeners and thixotropic agents in the suspension concentratesaccording to the invention is generally between 0.1 and 5% by weight, inparticular between 0.2 and 3% by weight.

Colorants and fragrances are known to the person skilled in the art.

Depending on the intended use, i.e. depending on which harmful plantsare to be controlled in the crop plants in question, the aqueoussuspension concentrates according to the invention also comprise afurther agrochemically active compound, preferably from the group of theherbicides. This further herbicidally active compound may both bepresent in the aqueous suspension concentrate according to the inventionas a ready formulation and be applied as a tank mix by joint dilution ofthe separately formulated or partially separately formulated components.

Particularly suitable for the aqueous suspension concentrates accordingto the invention are the active compounds A1 to A16 of formula (1): (I)

No. R¹ R² R³ R⁴ A1 ethyl ethyl ethyl ethyl A2 ethyl ethyl ethyl methylA3 ethyl ethyl methyl ethyl A4 ethyl methyl ethyl ethyl A5 methyl ethylethyl ethyl A6 ethyl ethyl methyl methyl A7 methyl ethyl ethyl methyl A8methyl methyl ethyl ethyl A9 ethyl methyl ethyl methyl A10 methyl ethylmethyl ethyl A11 ethyl methyl methyl ethyl A12 methyl methyl methylmethyl A13 methyl methyl methyl ethyl A14 methyl methyl ethyl methyl A15methyl ethyl methyl methyl A16 ethyl methyl methyl methyl

Particularly suitable for the aqueous suspension concentrates accordingto the invention are the active compounds B1 to B4 of formula (II): (II)

No. R⁵ R⁶ B1 isopropyl hydrogen B2 isopropyl chlorine B3 cyclopropylhydrogen B4 cyclopropyl chlorine

Particularly suitable for the aqueous suspension concentrates accordingto the invention are the active compounds C1 to C3 of formula (III):(III)

No. Q R⁷ R⁸ R⁹ C1

Cl CH₂OCH₂CF₃ SO₂CH₃ C2

SO₂CH₃ H CF₃ C3

SO₂CH₃ H CF₃

Suspension concentrates according to the invention comprising thecomponents A and B or A, B and C mentioned below may be mentioned aspreferred examples, without this constituting a limitation. A1 + B1 A2 +B1 A3 + B1 A4 + B1 A5 + B1 A6 + B1 A7 + B1 A8 + B1 A9 + B1 A10 + B1 A11 + B1  A12 + B1  A13 + B1  A14 + B1  A15 + B1  A16 + B1  A1 + B2 A2 +B2 A3 + B2 A4 + B2 A5 + B2 A6 + B2 A7 + B2 A8 + B2 A9 + B2 A10 + B2 A11 + B2  A12 + B2  A13 + B2  A14 + B2  A15 + B2  A16 + B2  A1 + B3 A2 +B3 A3 + B3 A4 + B3 A5 + B3 A6 + B3 A7 + B3 A8 + B3 A9 + B3 A10 + B3 A11 + B3  A12 + B3  A13 + B3  A14 + B3  A15 + B3  A16 + B3  A1 + B4 A2 +B4 A3 + B4 A4 + B4 A5 + B4 A6 + B4 A7 + B4 A8 + B4 A9 + B4 A10 + B4 A11 + B4  A12 + B4  A13 + B4  A14 + B4  A15 + B4  A16 + B4  A1 + B1 + C1A1 + B2 + C1 A1 + B3 + C1 A1 + B4 + C1 A1 + B1 + C2 A1 + B2 + C2 A1 +B3 + C2 A1 + B4 + C2 A1 + B1 + C3 A1 + B2 + C3 A1 + B3 + C3 A1 + B4 + C3A2 + B1 + C1 A2 + B2 + C1 A2 + B3 + C1 A2 + B4 + C1 A2 + B1 + C2 A2 +B2 + C2 A2 + B3 + C2 A2 + B4 + C2 A2 + B1 + C3 A2 + B2 + C3 A2 + B3 + C3A2 + B4 + C3 A3 + B1 + C1 A3 + B2 + C1 A3 + B3 + C1 A3 + B4 + C1 A3 +B1 + C2 A3 + B2 + C2 A3 + B3 + C2 A3 + B4 + C2 A3 + B1 + C3 A3 + B2 + C3A3 + B3 + C3 A3 + B4 + C3 A4 + B1 + C1 A4 + B2 + C1 A4 + B3 + C1 A4 +B4 + C1 A4 + B1 + C2 A4 + B2 + C2 A4 + B3 + C2 A4 + B4 + C2 A4 + B1 + C3A4 + B2 + C3 A4 + B3 + C3 A4 + B4 + C3 A5 + B1 + C1 A5 + B2 + C1 A5 +B3 + C1 A5 + B4 + C1 A5 + B1 + C2 A5 + B2 + C2 A5 + B3 + C2 A5 + B4 + C2A5 + B1 + C3 A5 + B2 + C3 A5 + B3 + C3 A5 + B4 + C3 A6 + B1 + C1 A6 +B2 + C1 A6 + B3 + C1 A6 + B4 + C1 A6 + B1 + C2 A6 + B2 + C2 A6 + B3 + C2A6 + B4 + C2 A6 + B1 + C3 A6 + B2 + C3 A6 + B3 + C3 A6 + B4 + C3 A7 +B1 + C1 A7 + B2 + C1 A7 + B3 + C1 A7 + B4 + C1 A7 + B1 + C2 A7 + B2 + C2A7 + B3 + C2 A7 + B4 + C2 A7 + B1 + C3 A7 + B2 + C3 A7 + B3 + C3 A7 +B4 + C3 A8 + B1 + C1 A8 + B2 + C1 A8 + B3 + C1 A8 + B4 + C1 A8 + B1 + C2A8 + B2 + C2 A8 + B3 + C2 A8 + B4 + C2 A8 + B1 + C3 A8 + B2 + C3 A8 +B3 + C3 A8 + B4 + C3 A9 + B1 + C1 A9 + B2 + C1 A9 + B3 + C1 A9 + B4 + C1A9 + B1 + C2 A9 + B2 + C2 A9 + B3 + C2 A9 + B4 + C2 A9 + B1 + C3 A9 +B2 + C3 A9 + B3 + C3 A9 + B4 + C3 A10 + B1 + C1  A10 + B2 + C1  A10 +B3 + C1  A10 + B4 + C1  A10 + B1 + C2  A10 + B2 + C2  A10 + B3 + C2 A10 + B4 + C2  A10 + B1 + C3  A10 + B2 + C3  A10 + B3 + C3  A10 + B4 +C3  A11 + B1 + C1  A11 + B2 + C1  A11 + B3 + C1  A11 + B4 + C1  A11 +B1 + C2  A11 + B2 + C2  A11 + B3 + C2  A11 + B4 + C2  A11 + B1 + C3 A11 + B2 + C3  A11 + B3 + C3  A11 + B4 + C3  A12 + B1 + C1  A12 + B2 +C1  A12 + B3 + C1  A12 + B4 + C1  A12 + B1 + C2  A12 + B2 + C2  A12 +B3 + C2  A12 + B4 + C2  A12 + B1 + C3  A12 + B2 + C3  A12 + B3 + C3 A12 + B4 + C3  A13 + B1 + C1  A13 + B2 + C1  A13 + B3 + C1  A13 + B4 +C1  A13 + B1 + C2  A13 + B2 + C2  A13 + B3 + C2  A13 + B4 + C2  A13 +B1 + C3  A13 + B2 + C3  A13 + B3 + C3  A13 + B4 + C3  A14 + B1 + C1 A14 + B2 + C1  A14 + B3 + C1  A14 + B4 + C1  A14 + B1 + C2  A14 + B2 +C2  A14 + B3 + C2  A14 + B4 + C2  A14 + B1 + C3  A14 + B2 + C3  A14 +B3 + C3  A14 + B4 + C3  A15 + B1 + C1  A15 + B2 + C1  A15 + B3 + C1 A15 + B4 + C1  A15 + B1 + C2  A15 + B2 + C2  A15 + B3 + C2  A15 + B4 +C2  A15 + B1 + C3  A15 + B2 + C3  A15 + B3 + C3  A15 + B4 + C3  A16 +B1 + C1  A16 + B2 + C1  A16 + B3 + C1  A16 + B4 + C1  A16 + B1 + C2 A16 + B2 + C2  A16 + B3 + C2  A16 + B4 + C2  A16 + B1 + C3  A16 + B2 +C3  A16 + B3 + C3  A16 + B4 + C3 

Preference is also given to aqueous suspension concentrates according tothe invention of the abovementioned combinations of the active compoundsA and B or A, B and C in each case as a mixture with one or moredispersants from the group consisting of tristyrylphenol polyethyleneglycol phosphoric esters, alkyl polyglycosides and alkyl polyglucosides.

In a preferred embodiment, the aqueous suspension concentrates accordingto the invention comprise

A) from 4 to 30% of a herbicidally active compound A1 to A16 of theformula (I),

B) from 4 to 30% of a safener B1 to B4 of the formula (II),

C) from 0 to 35% of a herbicidally active compound C1 to C3 of theformula (III),

D) from 0.5 to 30% of one or more dispersants,

E) from 30 to 70% of water,

F) from 1 to 15% of one or more antifreeze agents,

G) from 0.05 to 1% of one or more preservatives,

H) from 0.05 to 1% of one or more defoamers,

I) from 0.1 to 5% of one or more thickeners or thixotropic agents.

Particular preference is given to aqueous suspension concentratesaccording to the invention comprising

A) from 5 to 25% of a herbicidally active compound A1 to A16 of theformula (I),

B) from 5 to 25% of a safener B1 to B4 of the formula (II),

C) from 0 to 30% of a herbicidally active compound C1 to C3 of theformula (III),

D) from 1 to 20% of one or more dispersants,

E) from 35 to 65% of water,

F) from 2 to 10% of one or more antifreeze agents,

G) from 0.05 to 0.5% of one or more preservatives,

H) from 0.1 to 1% of one or more defoamers,

I) from 0.2 to 3% of one or more thickeners or thixotropic agents.

Very particular preference is given to aqueous suspension concentratesaccording to the invention comprising

A) from 5 to 20% of a herbicidally active compound A1 to A16, inparticular A12, of the formula (I),

B) from 8 to 20% of a safener B1 to B4, in particular B3, of the formula(II),

C) from 0 to 25% of a herbicidally active compound C1 to C3, inparticular C2, of the formula (III),

D) from 2.5 to 15% of one or more dispersants,

E) from 40 to 60% of water,

F) from 2 to 10% of one or more antifreeze agents,

G) from 0.05 to 0.25% of one or more preservatives,

H) from 0.1 to 0.5% of one or more defoamers,

I) from 0.25 to 2.5% of one or more thickeners or thixotropic agents.

All percentages are percent by weight.

Combinations of the active compounds of the formulae (I), (II) and(III), except for the combinations of

a) thiencarbazone-methyl, cyprosulfamide and tembotrione,

b) thiencarbazone-methyl, cyprosulfamide and isoxaflutole, and

c) thiencarbazone-methyl, cyprosulfamide and pyrasulfotole,

are per se novel and also form part of the subject matter of theinvention. These combinations are highly suitable for use as herbicidalcompositions. Particularly suitable for use as herbicidal compositionsare those comprising the components A, B and C of the following list:A1 + B1 + C1 A1 + B2 + C1 A1 + B3 + C1 A1 + B4 + C1 A1 + B1 + C2 A1 +B2 + C2 A1 + B3 + C2 A1 + B4 + C2 A1 + B1 + C3 A1 + B2 + C3 A1 + B3 + C3A1 + B4 + C3 A2 + B1 + C1 A2 + B2 + C1 A2 + B3 + C1 A2 + B4 + C1 A2 +B1 + C2 A2 + B2 + C2 A2 + B3 + C2 A2 + B4 + C2 A2 + B1 + C3 A2 + B2 + C3A2 + B3 + C3 A2 + B4 + C3 A3 + B1 + C1 A3 + B2 + C1 A3 + B3 + C1 A3 +B4 + C1 A3 + B1 + C2 A3 + B2 + C2 A3 + B3 + C2 A3 + B4 + C2 A3 + B1 + C3A3 + B2 + C3 A3 + B3 + C3 A3 + B4 + C3 A4 + B1 + C1 A4 + B2 + C1 A4 +B3 + C1 A4 + B4 + C1 A4 + B1 + C2 A4 + B2 + C2 A4 + B3 + C2 A4 + B4 + C2A4 + B1 + C3 A4 + B2 + C3 A4 + B3 + C3 A4 + B4 + C3 A5 + B1 + C1 A5 +B2 + C1 A5 + B3 + C1 A5 + B4 + C1 A5 + B1 + C2 A5 + B2 + C2 A5 + B3 + C2A5 + B4 + C2 A5 + B1 + C3 A5 + B2 + C3 A5 + B3 + C3 A5 + B4 + C3 A6 +B1 + C1 A6 + B2 + C1 A6 + B3 + C1 A6 + B4 + C1 A6 + B1 + C2 A6 + B2 + C2A6 + B3 + C2 A6 + B4 + C2 A6 + B1 + C3 A6 + B2 + C3 A6 + B3 + C3 A6 +B4 + C3 A7 + B1 + C1 A7 + B2 + C1 A7 + B3 + C1 A7 + B4 + C1 A7 + B1 + C2A7 + B2 + C2 A7 + B3 + C2 A7 + B4 + C2 A7 + B1 + C3 A7 + B2 + C3 A7 +B3 + C3 A7 + B4 + C3 A8 + B1 + C1 A8 + B2 + C1 A8 + B3 + C1 A8 + B4 + C1A8 + B1 + C2 A8 + B2 + C2 A8 + B3 + C2 A8 + B4 + C2 A8 + B1 + C3 A8 +B2 + C3 A8 + B3 + C3 A8 + B4 + C3 A9 + B1 + C1 A9 + B2 + C1 A9 + B3 + C1A9 + B4 + C1 A9 + B1 + C2 A9 + B2 + C2 A9 + B3 + C2 A9 + B4 + C2 A9 +B1 + C3 A9 + B2 + C3 A9 + B3 + C3 A9 + B4 + C3 A10 + B1 + C1 A10 + B2 +C1 A10 + B3 + C1 A10 + B4 + C1 A10 + B1 + C2 A10 + B2 + C2 A10 + B3 + C2A10 + B4 + C2 A10 + B1 + C3 A10 + B2 + C3 A10 + B3 + C3 A10 + B4 + C3A11 + B1 + C1 A11 + B2 + C1 A11 + B3 + C1 A11 + B4 + C1 A11 + B1 + C2A11 + B2 + C2 A11 + B3 + C2 A11 + B4 + C2 A11 + B1 + C3 A11 + B2 + C3A11 + B3 + C3 A11 + B4 + C3 A12 + B1 + C1 A12 + B2 + C1 A12 + B4 + C1A12 + B1 + C2 A12 + B2 + C2 A12 + B4 + C2 A12 + B1 + C3 A12 + B2 + C3A12 + B4 + C3 A13 + B1 + C1 A13 + B2 + C1 A13 + B3 + C1 A13 + B4 + C1A13 + B1 + C2 A13 + B2 + C2 A13 + B3 + C2 A13 + B4 + C2 A13 + B1 + C3A13 + B2 + C3 A13 + B3 + C3 A13 + B4 + C3 A14 + B1 + C1 A14 + B2 + C1A14 + B3 + C1 A14 + B4 + C1 A14 + B1 + C2 A14 + B2 + C2 A14 + B3 + C2A14 + B4 + C2 A14 + B1 + C3 A14 + B2 + C3 A14 + B3 + C3 A14 + B4 + C3A15 + B1 + C1 A15 + B2 + C1 A15 + B3 + C1 A15 + B4 + C1 A15 + B1 + C2A15 + B2 + C2 A15 + B3 + C2 A15 + B4 + C2 A15 + B1 + C3 A15 + B2 + C3A15 + B3 + C3 A15 + B4 + C3 A16 + B1 + C1 A16 + B2 + C1 A16 + B3 + C1A16 + B4 + C1 A16 + B1 + C2 A16 + B2 + C2 A16 + B3 + C2 A16 + B4 + C2A16 + B1 + C3 A16 + B2 + C3 A16 + B3 + C3 A16 + B4 + C3

Very particularly suitable are herbicidal compositions comprising thecomponents A12 + B1 + C1 A12 + B2 + C1 A12 + B3 + C1 A12 + B4 + C1 A12 +B1 + C2 A12 + B2 + C2 A12 + B4 + C2 A12 + B1 + C3 A12 + B2 + C3 A12 +B3 + C3 A12 + B4 + C3.

The abovementioned formulation auxiliaries of groups d) and f) to i) areknown to the person skilled in the art and are described, for example,in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2ndEd., Darland Books, Caldwell N.J., H.v. Olphen, “Introduction to ClayColloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden,“Solvents Guide”; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's“Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.;Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ.Co. Inc., N.Y. 1964; Schönfeldt, “Grenzflächenaktive Äthylenoxidaddukte[Surface-active ethylene oxide adducts]”, Wiss. Verlagsgesell.,Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie [Chemicaltechnology]”, volume 7, C. Hauser Verlag Munich, 4th Ed. 1986.

For use, the aqueous suspension concentrates or herbicidal compositionsaccording to the invention can be diluted in a customary manner, forexample with water or with aqueous solutions of fertilizers, such asammonium hydrogensulfate. It may be advantageous to add, to theresulting spray liquors, further agrochemically active compounds (forexample components for tank mixes in the form of suitable formulations)and/or customary auxiliaries and additives conventionally used forapplication and/or fertilizers. It has been found to be advantageous todilute the aqueous suspension concentrates or herbicidal compositionsaccording to the invention with aqueous solutions of fertilizers, forexample ammonium nitrate and ammonium sulfate.

The present invention accordingly also provides those aqueous suspensionconcentrates or herbicidal compositions comprising the agrochemicallyactive compounds, auxiliaries and additives and/or fertilizers mentionedin the above section.

The aqueous suspension concentrates and herbicidal compositionsaccording to the invention have outstanding herbicidal activity againsta broad spectrum of economically important monocotyledonous anddicotyledonous harmful plants. They even effect good control ofperennial problem weeds which emerge from rhizomes, root stocks or otherperennial organs.

The aqueous suspension concentrates and herbicidal compositionsaccording to the invention have prolonged herbicidal activity withprompt onset.

Although the aqueous suspension concentrates and herbicidal compositionsaccording to the invention have an outstanding herbicidal activityagainst monocotyledonous and dicotyledonous weeds, crop plants ofeconomically important crops, for example dicotyledonous crops such assoybeans, cotton, oilseed rape, sugar beet, or graminaceous crops suchas wheat, barley, rye, oats and millet, sugar cane, coffee, tea, cocoa,coconut, bananas or corn only suffer minor damage, if any. This is whythe aqueous suspension concentrates and herbicidal compositionsaccording to the invention are highly suitable for the selective controlof unwanted vegetation in plantations of agriculturally useful crops, inparticular in corn crops, or in ornamental plantations.

By virtue of their herbicidal properties, the aqueous suspensionconcentrates and herbicidal compositions according to the invention canalso be employed for controlling harmful plants in crops of geneticallymodified plants which are known or yet to be developed. In general, thetransgenic plants have specific advantageous properties, for exampleresistances to certain pesticides, especially certain herbicides,resistances to plant diseases or pathogens causing plant diseases, suchas certain insects or microorganisms, such as fungi, bacteria orviruses. Other specific properties relate, for example, to quantity,quality, storability, composition and specific constituents of theharvested material. Thus, transgenic plants having an increased starchcontent or modified starch quality or else having a different fatty acidcomposition of the harvested material, are known.

Preferred is the use of the aqueous suspension concentrates andherbicidal compositions according to the invention in economicallyimportant transgenic crops of useful plants and ornamentals, for examplegraminaceous crops, such as wheat, barley, rye, oats, millet, rice andcorn, in particular corn, or else crops of sugar beet, cotton, soybean,oilseed rape, potato, tomato, pea and other vegetables. The aqueoussuspension concentrates and herbicidal compositions according to theinvention can be employed as herbicides in crops of useful plants whichare resistant, or which have been made resistant by means of geneticengineering, to the phytotoxic effects of the herbicidally activecompounds.

When the aqueous suspension concentrates and herbicidal compositionsaccording to the invention are applied in transgenic crops, effects arefrequently observed which are specific for the application in thetransgenic crop in question, for example a modified, or specificallybroadened, spectrum of weeds which can be controlled, modifiedapplication rates which can be employed for the application, preferablygood combining ability with the herbicides to which the transgenic cropis resistant, and an effect on the growth and yield of the transgeniccrop plants, in addition to the effects, against harmful plants, whichcan be observed in the other crops.

The present invention furthermore also provides a method for controllingunwanted vegetation, preferably in crop plants such as cereals (forexample wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugarcane, oilseed rape, cotton and soybeans, particularly preferably inmonocotyledonous crops, such as cereals, for example wheat, barley, rye,oats, their hybridization products, such as triticale, rice, corn andmillet, one or more aqueous suspension concentrates or herbicidalcompositions according to the invention being applied to the harmfulplants, parts of plants, plant seeds or the area in which the plantsgrow, for example the area under cultivation.

The plant crops can also have been genetically modified or have beenobtained by mutation selection and are preferably tolerant toacetolactate synthase (ALS) inhibitors.

The aqueous suspension concentrates according to the invention areprepared in a manner known to the person skilled in the art, for exampleby mixing the individual constituents; see, in this context,Winnacker-Küchler, “Chemische Technologie”, volume 7, C. Hauser VerlagMunich, 4th Ed. 1986, Wade van Valkenburg, “Pesticide Formulations”,Marcel Dekker, N.Y., 1973; K. Martens, “Spray Drying” Handbook, 3rd Ed.1979, G. Goodwin Ltd. London.

The examples below illustrate the invention. The surfactants andauxiliaries used in this context mean:

-   Dispergon® LFH=tristyrylphenol polyethylene glycol phosphoric ester,    supplier: CLARIANT-   Agnique® PG 9116=C₉- to C₁₁-alkyl glucopyranoside, supplier: COGNIS-   AL 2575=alkyl polyglucoside, supplier: UNIQEMA-   Rhodorsil® 416=defoamer based on polydimethylsiloxane, supplier:    RHODIA-   Acticide® MBS=mixture of 2-methyl-2H-isothiazol-3-one and    1,2-benzisothiazol-3(2H)-one supplier: THOR-   Proxel® GXL=sodium salt of 1,2-benzisothiazol-3(2H)-one supplier:    ZENECA-   Aerosil® 200=silicon dioxide, chemically obtained supplier: Degussa-   Attagel® 50=magnesium aluminum hydrosilicate supplier:    CHEMIE-MINERALIEN GMBH-   VanGel® B=hydrated magnesium aluminum silicate supplier: VANDERBILT    INC., ERBSLÖH KG

WORKING EXAMPLES

The preparation procedure described below relates to the recipes ofexamples 1 to 4 mentioned below:

Water is initially charged in a stirred tank. With stirring, defoamers,dispersants, preservatives and antifreeze agents, herbicides andsafeners are added, and stirring is continued for a short while.Thickeners and thixotropic agents are then added. The suspensionobtained in this manner is subjected to coarse pregrinding in a colloidmill and then ground in a glass bead mill using glass beads of adiameter of 1 mm until the mean particle size is 1 to 2 micron. Duringgrinding, the suspension is kept at a temperature of at most 25° C.using external cooling. EXAMPLE 1 A) 7.95 g herbicide A12 B) 13.16 gsafener B3 C) 19.32 g herbicide C2 D) 3.00 g Dispergon ® LFH D) 2.00 gAL 2575 E) 46.57 g water F) 7.00 g propylene glycol G) 0.10 g Proxel ®GXL H) 0.25 g Rhodorsil ® 416 I) 0.65 g Aerosil ® 200

EXAMPLE 2 A) 7.95 g herbicide A12 B) 13.16 g safener B3 C) 19.32 gherbicide C2 D) 3.00 g Dispergon ® LFH D) 2.00 g Agnique ® PG 9116 E)46.57 g water F) 7.00 g propylene glycol G) 0.10 g Proxel ® GXL H) 0.25g Rhodorsil ® 416 I) 0.65 g Aerosil ® 200

EXAMPLE 3 A) 20.21 g herbicide A12 B) 20.08 g safener B3 D) 3.00 gDispergon ® LFH D) 1.00 g AL 2575 E) 47.36 g water F) 7.00 g propyleneglycol G) 0.10 g Proxel ® GXL H) 0.25 g Rhodorsil ® 416 I) 0.50 gAttagel ® 50 I) 0.50 g VanGel ® B

EXAMPLE 4 A) 20.05 g herbicide A12 B) 20.08 g safener B3 D) 4.00 gDispergon ® LFH D) 1.00 g AL 2575 E) 46.32 g water F) 7.00 g propyleneglycol G) 0.10 g Proxel ® GXL H) 0.25 g Rhodorsil ® 416 I) 0.60 gAttagel ® 50 I) 0.60 g VanGel ® B

After storage for several months even at elevated temperature, theaqueous suspension concentrates according to the invention haveexcellent stability and do not have any tendency to flocculate or toblock spray nozzles.

WORKING EXAMPLES

Post-emergence Herbicidal Action

Seeds of monocotyledonous and dicotyledonous weeds and crop plants areplaced in sandy loam in wood fiber pots or in plastic pots, covered withsoil and grown in the greenhouse, during the vegetation period alsooutdoors outside of the greenhouse, under good growth conditions. 2 to 3weeks after sowing, the test plants, which are in the one to three-leafstage, are treated. The formulated herbicidal compositions are sprayedonto the plants and the soil surface in various dosages at a waterapplication rate of 300 I/ha (converted), with addition of wetting agent(0.2 to 0.3%). 3 to 4 weeks after the treatment of the test plants, theeffect of the preparations is scored visually in comparison to untreatedcontrols (herbicidal activity in percent (%): 100% activity=the plantshave died, 0% activity=like control plants).

Here, for example, the herbicidal compositions 1 to 4 exhibit, at anapplication rate of 320 g (sum of the three components A, B and C, in aratio of 1:1.65:2.43) per hectar, at least 90% activity against numerousharmful plants, such as Abutilon theophrasti, Alopecurus myosuroides,Amaranthus retroflexus, Avena fatua, Chenopodium album, Cyperusserotinus, Digitaria sanguinalis, Matricaria chamomilla, Setaria viridisand Veronica persica and less than 5% damage of crop plants, such ascorn. Herbicidal composition No. Component 1 A12 B3 C2 2 A12 B1 C2 3 A14B3 C2 4 A14 B1 C2

The effect of the safener substance can be assessed by comparison of theactivity of test substances on crop plants treated without and withsafener.

Here, it is found that the herbicidal activities of the compositionsaccording to the invention (100% and 99%, respectively) exceed thevalues expected according to Colby (in each case 85%) calculated usingthe formula below (cf. S. R. Colby; in Weeds 15 (1967) pp. 20 to 22):$E = {A + B - \frac{A \times B}{100}}$here:

A, B=activity of component A and B, respectively, in percent

E=expected value in percent

1. An aqueous suspension concentrate, comprising A) a herbicidallyactive compound of the formula (I) in suspended form

 in which R¹, R², R³ and R⁴ independently of one another are methyl orethyl, B) a safener of the formula (II),

 in which R⁵ is isopropyl or cyclopropyl and R⁶ is hydrogen or chlorine,C) optionally a herbicidally active compound of the formula (III),

 in which Q is a radical Q¹, Q² or Q³,

R⁷ is chlorine, methylsulfonyl or trifluoromethyl, R⁸ is hydrogen or2,2,2-trifluoroethoxymethyl, R⁹ is methylsulfonyl or trifluoromethyl, D)dispersants and E) water.
 2. The suspension concentrate as claimed inclaim 1, comprising dispersants from the group consisting oftristyrylphenol polyethylene glycol phosphoric esters, alkylpolyglycosides and alkyl polyglucosides.
 3. The suspension concentrateas claimed in claim 1, additionally comprising F) antifreeze agents G)preservatives H) defoamers I) thickeners and thixotropic agents.
 4. Thesuspension concentrate as claimed in claim 1, comprising A) from 4 to30% of a herbicidally active compound A1 to A16 of the formula (I), B)from 4 to 30% of a safener B1 to B4 of the formula (II), C) from 0 to35% of a herbicidally active compound C1 to C3 of the formula (III), D)from 0.5 to 30% of one or more dispersants, E) from 30 to 70% of water,F) from 1 to 15% of one or more antifreeze agents, G) from 0.05 to 1% ofone or more preservatives, H) from 0.05 to 1% of one or more defoamers,I) from 0.1 to 5% of one or more thickeners or thixotropic agents. 5.The suspension concentrate as claimed in claim 1, comprising A) from 5to 25% of a herbicidally active compound A1 to A16 of the formula (I),B) from 5 to 25% of a safener B1 to B4 of the formula (II), C) from 0 to30% of a herbicidally active compound C1 to C3 of the formula (III), D)from 1 to 20% of one or more dispersants, E) from 35 to 65% of water, F)from 2 to 10% of one or more antifreeze agents, G) from 0.05 to 0.5% ofone or more preservatives, H) from 0.1 to 1% of one or more defoamers,I) from 0.2 to 3% of one or more thickeners or thixotropic agents. 6.The suspension concentrate as claimed in claim 1, comprising A) from 5to 20% of a herbicidally active compound A1 to A16 of the formula (I),B) from 8 to 20% of a safener B1 to B4 of the formula (II), C) from 0 to25% of a herbicidally active compound C1 to C3 of the formula (III), D)from 2.5 to 15% of one or more dispersants, E) from 40 to 60% of water,F) from 2 to 10% of one or more antifreeze agents, G) from 0.05 to 0.25%of one or more preservatives, H) from 0.1 to 0.5% of one or moredefoamers, I) from 0.25 to 2.5% of one or more thickeners or thixotropicagents.
 7. A herbicidal composition, comprising in each case an activecompound of the formula (I), (II) and (III), except for combinations ofa) thiencarbazone-methyl, cyprosulfamide and tembotrione, b)thiencarbazone-methyl, cyprosulfamide and isoxaflutole, and c)thiencarbazone-methyl, cyprosulfamide and pyrasulfotole.
 8. An aqueousherbicidal composition, obtainable by diluting a suspension concentrateas claimed in 1 with water.
 9. An aqueous herbicidal composition,obtainable by diluting a suspension concentrate as claimed in claim 1with an aqueous solution of fertilizers.
 10. The aqueous herbicidalcomposition as claimed in claim 9, where the fertilizer is ammoniumsulfate or ammonium nitrate.
 11. A method for controlling unwantedvegetation comprising applying an effective amount of an aqueoussuspension concentrate as claimed in claim 1 to the plants, parts of theplants, the seed or the area in which the plants grow.
 12. An aqueousherbicidal composition, obtainable by diluting a herbicidal compositionas claimed in claim 7 with water.
 13. An aqueous herbicidal composition,obtainable by diluting a herbicidal composition as claimed in claim 7with an aqueous solution of fertilizers.
 14. An aqueous herbicidalcomposition, obtainable by diluting a herbicidal composition as claimedin claim 8 with an aqueous solution of fertilizers.
 15. A method forcontrolling unwanted vegetation comprising applying an effective amountof a herbicidal composition as claimed in claim 7 to the plants, partsof the plants, the seed or the area in which the plants grow.